A tpe composition that exhibits excellent adhesion to textile fibers-

ABSTRACT

A combination of a low flexural modulus and low crystallinity polyolefin and a functionalized polyolefin were found to result in an olefin composition with excellent adhesion to metals and polar polymers (e.g. polyesters, polyamides, etc) especially fibers therefrom. When these two polyolefins were added to a thermoplastic vulcanizate (e.g. used to partially or fully replace the semicrystalline polyolefin of a thermoplastic vulcanizate), the thermoplastic vulcanizate was found to have the necessary adhesion to form fiber reinforced thermoplastic vulcanizate.

FIELD OF INVENTION

[0001] A polyolefin composition and a thermoplastic elastomer based upona semi-crystalline polyolefin are described which have improved adhesionto polar polymers including textile fibers and metals including wires. Acombination of a low flexural modulus (low crystallinity) polypropyleneand a maleic anhydride functionalized polypropylene were found toexhibit excellent adhesion to textile fibers. Incorporation of these twocomponents into a TPE (thermoplastic elastomer) imparts excellentadhesion of the TPE to textile fibers.

BACKGROUND OF INVENTION

[0002] Polyolefins and thermoplastic elastomers rich in polyolefins havetraditionally had poor adhesion to textile fibers. Experiments withthermoplastic vulcanizates (TPV), a subset of thermoplastic elastomers(TPE), using formulations similar to those of U.S. Pat. Nos. 4,130,534and 4,130,535 resulted in peel strengths of only 0.5 to 1.0 pounds perlinear inch (pli) between the TPV and textile fibers after meltprocessing the TPV to the textile fibers. The industrial hose andbelting markets generally require a peel strength of at least 8 to 12pli for candidate matrix materials for fiber reinforced hoses andbelting. While polyolefins and TPVs from polyolefins have benefits overplasticized polyvinyl chloride resin (in terms of chemical resistanceand physical properties after aging) and over crosslinked rubbers (interms of processability and physical properties after aging) their usewith textile fibers has been limited due to low adhesion values (lowpeel strengths).

[0003] U.S. Pat. No. 4,957,968 teaches adhesive thermoplastic elastomerblends comprising a) at least a polyolefin modified by a chemicallyreactive functional group, b) at least one other polymer, and c) atleast one olefinic elastomer.

[0004] Typically, when a polymer and a fiber exhibit poor adhesiontoward each other, the problem is attributed to poor wetting of thefiber with the polymer or a lack of good interactions between the fibersurface and the polymer. If processing aids are not effective in solvingthe wetting problem, then different fibers or a different polymer ischosen or a sizing, more interactive with the specific polymer, isapplied to the fiber.

SUMMARY OF INVENTION

[0005] A combination of two polymers was found that improves theinteraction of polyolefins and/or thermoplastic vulcanizates (TPV) withmore polar polymers and metals, especially various textile fibers andmetal wires. More polar polymers are defined as those polymers morepolar than polyolefins due to the inclusion of heteroatoms such asoxygen or nitrogen in the repeating groups. The first polymer is a lowcrystallinity polyolefin with a low flexural modulus (tangent) such asfrom about 5,000 to about 20,000 psi (34.5 to 138 MPa). It ishypothesized that the low flexural modulus helps reduce stress at thebond line between the polyolefin and the fiber and/or polar polymer. Thefirst polymer may be characterized as a polyolefin polymer or copolymerwith only 10 to 30 percent crystallinity. As described later the firstpolymer with low crystallinity and a low modulus may be a blend (reactorblend, physical blend, etc.) of a very low crystallinity polymer with aconventional semi-crystalline polyolefin. The second polymer is afunctionalized polyolefin (e.g. semicrystalline polyolefin) with fromabout 0.5 to about 3.5 mole percent of functional repeating units.Preferred functional groups are carboxylic acid groups and/or anhydridefrom a di or poly carboxylic acid. For the purposes of this applicationthe polyolefin can be derived from polymerizing monoolefins or frompolymerizing diolefins and then hydrogenating them to obtain similarmicrostructures to polyolefins. These polyolefins from diolefins can beblock copolymers with other monomers such as stryene.

[0006] In some embodiments, the functionalized polyolefin and thepolyolefin with the low flexural modulus and low crystallinity are theonly required components of a hot-melt composition with excellentadhesion to polar polymers and textile fibers.

[0007] In another embodiment, a crosslinked rubber is present so thatthe rubbery properties of a thermoplastic vulcanizate are present.

[0008] In yet another thermoplastic vulcanizate embodiment, both aconventional high modulus polyolefin and rubber are present. The highmodulus polyolefin can increase the stiffness and/or increase thesoftening temperature of the composition for uses requiring stiffness orhaving a higher use temperature requiring a higher softening temperaturefor the TPV.

[0009] Any of the above compositions can be used to adhere to polarpolymers, metal, high tensile strength fibers and/or sheets. Theexcellent adhesion attributed to the combination of functionalizedpolyolefin and low crystallinity and low flexural modulus polyolefin iswell utilized in melt processing a thermoplastic vulcanizate around afiber or metal (e.g. wire) reinforced assembly.

[0010] Hydrosilylation crosslinking is a particularly advantageous typeof crosslinking for the rubber phase as it has minimal side reactionswith the functionalized polyolefin allowing the functionalizedpolyolefin to be blended with the other components before crosslinkingthe rubber phase.

DETAILED DESCRIPTION

[0011] The components of the invention vary depending on therequirements of the particular application. Two polymers are common toall applications. They are the low crystallinity, low flexural moduluspolyolefin and the functionalized polyolefin. Other components that canbe added are a rubber phase (usually crosslinked by dynamicvulcanization), an additional one or more semicrystalline polyolefinswith higher flexural modulus, and conventional additives to a hot-meltadhesive or thermoplastic vulcanizate.

[0012] The first polyolefin can also be described as a polyolefin withlow levels of crystallinity as compared to a highly isotacticsemicrystalline polypropylene. Desirably the first polyolefin has fromabout 10, 12, 14, or 15 to about 20, 25, 26.5, 30, or 32 weight percentcrystallinity. The weight percent crystallinity can be determined bydividing the heat of fusion of the sample as received by the heat offusion of 100% crystalline polypropylene (assumed to be 209 joules/g).The first polyolefin, with low flexural modulus (tangent), can generallybe any polyolefin with low polyolefin crystallinity and a flexuralmodulus desirably from about 5,000 to about 20,000 psi (34.5-138 MPa),more desirably from about 7,500 to about 17,500 psi (51.7-121 MPa) andpreferably from about 9,000 to about 16,000 psi (62 to 110.4 MPa). Theflexural modulus is measured by ASTM D 790A test method at 23° C.

[0013] The first polyolefin can be a homopolymer with low crystallinitydue to random or regular variations in tacticity, a copolymer that haslow crystallinity due to the comonomer(s) and/or random or regularvariations in tacticity (including blockly homo and copolymers), andpolymers prepared by blending or grafting together oligomers orpolymers. In particular, atactic and isotactic polypropylene (PP),in-situ blends, long isotactic PP sequence metallocene catalyszedethylene-propylene copolymers (EP's), elastic PPs with stereoblocks ofatactic PP and isotactic PP (which can be metallocene catalyzed),isotactic PPs with metallocene catalyzed asymmetrical stereoerrors,isotactic PP and atactic PP combinations by blending or by stereoblocksfrom mixed metallocenes, and PPs that have an atactic PP backbone withisotactic PP branches using metallocene catalysis. For the purpose ofthis application, both the terms polymer and copolymer will beinterpreted as including copolymers, terpolymers, etc., so that polymerincludes copolymer and copolymer includes a polymer from three or moremonomers. Desirably, at least 70, 80, or 90 weight percent of the repeatunits are from olefin monomers having from 2 to 8 carbon atoms andpreferably at least 70, 80, or 90 weight percent are derived frompropylene monomer. Examples of operative low flexural modulus, lowcrystallinity polymers are Rexflex® 101 from Huntsman in Houston, Texas,characterized as a reactor blend of atactic and isotactic propylenehomopolymer having about 10 to about 20 wt. % crystallinity and Adflex®KS 357P from Montell North America in Wilmington, Del., characterized asa polyolefin with low weight percent crystalline content of 10 to 20 wt,%.

[0014] When the first polyolefin with low crystallinity and low flexuralmodulus is used in a thermoplastic vulcanizate, it is desirably used inan amount from about 10 to about 400 parts by weight and more desirablyfrom about 12.5 or 15 to about 350 or 400 parts by weight per 100 partsby weight of total rubber in the TPV. It is also desirable that thepolyolefin with low crystallinity and low flexural modulus be presentfrom about 10 to about 350 parts by weight and more desirably from about15 to about 75 or 85 parts by weight per 100 total parts ofsemi-crystalline polyolefin in the thermoplastic phase. When thepolyolefin with low crystallinity and low flexural modulus is used in anon-TPV application, then it is desirably present in an amount fromabout 20 to about 90 parts by weight and more desirably from about 25 toabout 75 or 85 parts by weight per 100 parts by weight totalpolyolefins.

[0015] For the purpose of this application the total semicrystallinepolyolefins includes the functionalized polyolefin if it has greaterthan 26.5 or 30 weight percent crystallinity.

[0016] In lieu of the polyolefin with low crystallinity and low flexuralmodulus one may be able to use a generally amorphous polyolefin (apolyolefin having less than 10 weight percent crystallinity andpreferably less than 3 weight percent crystallinity) which will blendwith a semicrystalline polyolefin such as isotactic polypropylene. Thisgenerally amorphous polyolefin is different than EPDM rubber in that itdesirably has at least 75 mole percent and more desirably at least 80,85, or 90 mole percent repeating units from a single olefin monomer,preferably propylene. This substitution is taught in WO 97/39059 as analternative for the products marketed under the Rexene™ and Rexflex™names. When the amorphous polyolefin is used in lieu of a lowcrystallinity polyolefin it should be used in an amount from about 5 toabout 200 parts by weight, more desirably from about 6 or 7.5 to about125 or 150 parts by weight per 100 parts total weight of rubber in theTPV. When the amorphous polyolefin is used in lieu of a lowcrystallinity polyolefin it should be used in an amount from about 5 toabout 75 parts by weight, more desirably from about 7.5 to about 37 or43 parts by weight per 100 parts total weight of semi-crystallinepolyolefins in the thermoplastic phase. For the purpose of thisapplication polyolefins with less than 10 weight percent crystallinitywill be considered as amorphous.

[0017] The functionalized polyolefin desirably has from about 0.5 toabout 3.5 mole percent functional groups, and more desirably from about1 or 1.5 to about 2.0 or 2.5 mole percent functional groups based upontotal repeating units in the polymer. The functional groups may be frommonomers copolymerized with the olefin monomers or may be added bypost-polymerization functionalization such as by grafting unsaturatedmonomers onto polyolefins as documented by U.S. Pat. No. 5,637,410 to BPChemicals Limited which describes carboxylic acid grafting in columns 1and 2. Desirably, at least 70, 80, or 90 weight percent of the repeatingunits for this polyolefin are olefin monomers of 2 to 8 carbon atoms andmore preferably 2 or 3 carbon atoms. For the purposes of thisapplication, functional groups will be defined as groups withheteroatoms other than carbon and hydrogen. Examples of functionalgroups include carboxylic acid groups, anhydrides from dicarboxylic orpolycarboxylic acids, such as the group derived from grafting maleicanhydride to a polyolefin backbone. Preferred groups are carboxylic acidgroups or anhydrides of two or more carboxylic acids. Thus thefunctionalized polyolefin can be a copolymer of acrylic acid andethylene or propylene; a terpolymer of ethylene, vinyl acetate andacrylic acid; or a terpolymer of ethylene, methyl acrylate, acrylicacid; etc.

[0018] The polyolefin which is functionalized to make the functionalizedpolyolefin is desirably made from monoolefins so that it is compatiblewith the semicrystalline polyolefin phase. However there are otherpolymers having hydrogenated blocks made from from diolefins (e.g.conjugated dienes having from 4 to 8 carbon atoms) which polymer blocksare chemically indistinguishable from polyolefins polymerized frommonoolefins by chemical analysis and have compatibility with thesemicrystalline polymers made from monoolefins due to the similaritiesof their microstructure and their composition. For the purposes of thisapplication these block copolymers with blocks of hydrogenatedpolydienes will be defined as polyolefins due to their equivalence toconventional polyolefins made from monoolefins. These polymers includehomopolymers and block copolymers comprising blocks of polydiene thatare subsequently hydrogenated. Blocks of hydrogenated polyisoprene looklike perfectly random copolymers of ethylene and propylene. Blocks ofhydrogenated polybutadiene look like copolymers of 1,2-butylene andethylene. Commercially available hydrogenated blocky copolymers ofdienes and styrene can function as the starting material forfunctionalized polyolefins due to the equivalence of the hydrogenateddiene blocks to a polyolefin made from monoolefins. The polymer backboneof the functionalized material can also be a maleic anhydride modifiedhydrogenated styrene/butadiene/styrene (SBS) and/or hydrogenatedstyrene/butadiene/styrene (SEBS).

[0019] When the functionalized polyolefin is used in a thermoplasticvulcanizate (TPV) it is desirably used in an amount from about 10 or 15to about 200 parts by weight, more desirably from about 15 or 20 toabout 100 or 200 and preferably from about 40 to about 80 parts byweight per 100 parts by weight of rubbers in the TPV. It is alsodesirable that the functionalized polyolefin be present in an amountfrom about 10 to about 60 parts by weight and more desirably from about12.5 to about 50 parts by weight per 100 total parts of polyolefin inthe thermoplastic phase. When the functionalized polyolefin is used in anon-TPV application, it is desirably present in an amount from about 5to about 60 parts by weight and more desirably from about 10 to about 50parts by weight per 100 parts by weight total polyolefins.

[0020] A second semicrystalline polyolefin with higher flexural moduluscan optionally be used in any of the embodiments. The higher flexuralmodulus is higher than the polyolefin with low crystallinity and lowflexural modulus. This higher flexural modulus polymer desirably has aflexural modulus measured by ASTM D 790A of at least 30,000 psi (205MPa) and more desirably at least 45,000 psi (310 MPa). The polymer canbe made by any known polymerization process including low pressure andhigh pressure processes. The monomers are desirably olefins having from2 to 8, 10, or 12 carbon atoms. Desirably, the second semicrystallinepolyolefin has at least 70, 80, or 90 weight percent of repeat unitsfrom olefin monomers with the residual repeat units, if any, selectedfrom copolymerizable monomers. The second semicrystalline polyolefin maybe present to increase the amount of the polyolefin phase, which may bedesirable to increase the processability of the composition or thehardness of the composition. The amount of a second semicrystallinepolyolefin in a TPV, when present, is desirably in amounts up to 300parts by weight and more desirably from about 5 to about 200, 250 or 300parts by weight per 100 parts by weight of rubber. Desirably, inapplications requiring the elastic properties of a TPV, the totalpolyolefins (polyolefin with low flexural modulus, functionalizedpolyolefin, and optional second polyolefin) are present in amount fromabout 20 to about 450 parts by weight per 100 parts by weight of rubber.

[0021] For the purposes of this application the semicrystallinepolyolefins will include polyolefins with a at least 26.5 wt, %crystallinity. The functionalized polyolefin and any othersemicrystalline polyolefins will be included in calculations for totalsemicrystalline polyolefins provided they have at least 26.5 wt, %crystallinity. It will not include rubbers such as EPDM rubber, which isa polyolefin but is generally defined as amorphous or essentiallynon-crystalline.

[0022] The rubber component can be any rubber suitable for use in athermoplastic vulcanizate. These rubbers includeethylene-propylene-diene rubber (EPDM) (e.g. copolymer of two or morealphamonoolefins in weight ratios of 25:75 to 75:25 [if three or moremonoolefins are used the then two have to be each be present in anamount of at least 25 weight percent of the total] with 0.2 to 10 wt %of repeating units from a polyene with 5 to 15 carbon atoms based on theweight of the EPDM); various isobutylene copolymers such as butyl rubbercopolymers of isobutylene and p-methylstyrene, butyl rubber copolymersof isobutylene and a diene (including brominated and chlorinatedversions), and copolymers or terpolymers of isobutylene and divinylaromatic monomers; natural rubber; homopolymers of conjugated dieneshaving from 4 to 8 carbon atoms, optionally including halogens, such aspolybutadiene, synthetic isoprene, and chloroprene rubber; or copolymershaving at least 50 weight percent repeating units from said conjugateddienes, such as styrene-butadiene rubber and/or nitrile rubber: andcombinations thereof.

[0023] While the description above is generally adequate for the rubbersin general in thermoplastic vulcanizates, in some embodiments usinghydrosilylation crosslinking the preferred rubbers are as set forthbelow. Hydrosilylation crosslinking is taught in U.S. Pat. Nos.4,803,244 and 5,672,660 hereby incorporated by reference. The preferredrubbers are those with residual carbon to carbon double bondunsaturation that is pendant to the polymer backbone and stericallyunhindered with respect to reaction with the hydrosilylationcrosslinking agent. Preferred rubbers with such sterically unhinderedbonds react quickly with low concentrations of hydrosilylationcrosslinking agent and low concentrations of catalyst.

[0024] Preferred rubbers for hydrosilylation crosslinking includerubbers from two or more α-monoolefins, copolymerized with a polyene,usually a non-conjugated diene such as EPDM rubber, previouslydescribed. Useful polyenes include 5-ethylidene-2-norbornene (ENB);1,4-hexadiene (HD); 5-5 methylene-2-norbornene (MNB); 1,6-octadiene;5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; 1,3-cyclopentadiene;1,4-cyclohexadiene; dicyclopentadiene (DCPD); 5-vinyl-2-norbornene (VNB)and the like, or a combination thereof. 5-vinyl-2-norbornene (VNB) is apreferred polyene in EPBM for hydrosilylation crosslinking.

[0025] Another preferred rubber for hydrosilylation crosslinking is acopolymer or terpolymer of isobutylene and divinyl aromatic compounds.These polymers are described in U.S. Pat. Nos. 4,916,180 and 2,671,774,hereby incorporated by reference. These polymers desirably comprise fromabout 94 to about 99 or 99.5 weight percent repeating units fromisobutylene, from about 0 or 0.5 to about 3 or 5 weight percentrepeating units from a conjugated diene and from about 0.5 to about 3 or5 weight percent repeating units from a divinyl aromatic monomer havingthe formula

[0026] wherein X is an aromatic (aryl) or an alkyl substituted aromaticmoiety, and each R may be the same or different and is selected fromhydrogen or a C₁₋₅ alkyl. Divinyl benzene is a preferred example of theabove divinyl aromatic monomer.

[0027] Another preferred rubber is a copolymer of isobutylene andpara-methylstyrene which is post-polymerization functionalized with ahalogen on the paramethyl group and then functionalized by replacing thehalogen with an acrylic or alkacrylic group. This type of substitutionchemistry on copolymers of isobutylene and para-methylstyrene is taughtin U.S. Pat. No. 5,162,445 hereby incorporated by reference. Thisaddition of the acrylic or alkacrylic group is well known to the art andinvolves the reaction of

[0028] where M⁺ is a metal ion such as Na⁺ or K⁺ and Br is bromine, anexample of a halogen, the remainder of the isobutylene-paramethylstyreneis represented by the squiggly line, and each R group is independently Hor an alkyl or alkylene of 1 to 4 carbon atoms. The product is

[0029] The curative or crosslinking system for the rubber can be anysystem conventionally used for thermoplastic vulcanizates. These includeperoxide, azide, sulfur, phenolic resin and acceleratedsulfur-vulcanizing agents. The combination of maleimide and disulfideaccelerator can be used. Other curatives such as those used for butylrubber include sulfur, phenolic resin, metal oxide, p-quinone dioxime,or bis-maleimide vulcanizing system. Halogenated butyl rubbers can becrosslinked with zinc oxide. The curatives or crosslinking systems areused in conventional amounts for crosslinking the rubber based upon theweight of the rubber component.

[0030] Alternatively, the crosslinking system can comprise ahydrosilylation crosslinking system such as described in U.S. Pat. Nos.4,803,244 and 5,672,660, hereby incorporated by reference. Preferredsilicon hydride compounds (hydrosilylation crosslinkers) includecompounds of the formula

[0031] wherein each R is independently selected from the groupconsisting of alkyls comprising 1 to 20 carbon atoms, cycloalkylscomprising 4 to 12 carbon atoms and aryls. In formula (1) it ispreferred that each R be independently selected from a group consistingof alkyls comprising 1 to 6 carbon atoms. Even more preferred isR=methyl, R′ represents a hydrogen atom, an alkyl or alkoxy group havingfrom 1 to about 24 carbon atoms. R″ represents R or a hydrogen atom.

[0032] m is an integer having a value ranging from 1 to 50, n is aninteger having a value ranging from 1 to 50, and p is an integer havinga value ranging from 0 to 6.

[0033] Particularly preferred polyorganosiloxanes are those in which thesilicon atom of the silicon hydride functionality is bound byheteroatoms/atoms having lone pairs of electrons. The preferredpolyorganosiloxanes may also be substituted with appropriatefunctionality permitting solubility in the reaction media. A type ofthis functionalization is described in U.S. Pat. No. 4,046,930, whichteaches alkylation of polyorganosiloxanes. The weight percent ofalkylation should be limited to a level that permits adequate reactionrates and minimizes steric constraints.

[0034] The amount of silicon hydride compound useful in the process ofthe present invention can range from about 0.1 to about 10.0 moleequivalents of SiH per mole of carbon-carbon double bond in the rubber,and preferably is in the range of about 0.5 to about 5.0 moleequivalents of SiH per carbon-carbon double bond in the rubber componentof the thermoplastic elastomer.

[0035] It has generally been understood that any hydrosilylationcatalyst, or catalyst precursor capable of generating a catalyst insitu, which will catalyze the hydrosilylation reaction with thecarbon-carbon bonds of the rubber, can be used. Such catalysts haveincluded transition metals of Group VIII such as palladium, rhodium,platinum and the like, including complexes of these metals.Chloroplatinic acid has been disclosed as a useful catalyst in U.S. Pat.No. 4,803,244 and European Application No. 651,009, which furtherdisclose that the catalyst may be used at concentrations of 5 to 10,000parts per million parts by weight rubber and 100 to 200,000 parts permillion parts by weight rubber, respectively.

[0036] Significantly lower concentrations of platinum-containingcatalyst can be used, while obtaining improvement in both the speed ofthe reaction and the efficiency of the crosslinking. Concentrations ofcatalyst in the range of about 0.01 to about 20, 40 or 50 parts permillion parts by weight of rubber, expressed as platinum metal, incombination with a diene-containing rubber having carbon-carbon multiplebonds which are predominately sterically unhindered, are effective inrapidly and completely curing the rubber in the process of dynamicallyvulcanizing blends of thermoplastic resin and rubber. Catalystconcentrations of about 0.1 to about 4 or 40 parts per million by weightexpressed as platinum metal, and based on the weight of rubber, areparticularly preferred.

[0037] Platinum-containing catalysts, which are useful in the process ofthe invention, are described, for example, in U.S. Pat. Nos. 4,578,497;3,220,972; and 2,823,218, all of which are incorporated herein by thisreference. These catalysts include chloroplatinic acid withsymdivinyltetramethyldisiloxane, dichloro-bis (triphenylphosphine)platinum (II), cis-dichloro-bis (acetonitrile) platinum (II),dicarbonyldichloroplatinum (II), platinum chloride and platinum oxide.Zero valent platinum metal complexes such as Karstedt's catalyst areparticularly preferred.

[0038] In order for the catalyst to function most efficiently in thedynamic vulcanization environment, it is important that it is inherentlythermally stable, or that its activity is inhibited to prevent too rapida reaction or catalyst decomposition. Appropriate catalyst inhibitorsthat are suitable to stabilize the platinum catalyst at high temperatureinclude 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane and its higheranalogs such as vinyl cyclic pentamer. However, other olefins that arestable above 165° C. are also useful. These include maleates, fumaratesand the cyclic pentamer. It is also particularly preferred in theinvention to use a catalyst that remains soluble in the reaction medium.

[0039] The thermoplastic elastomer may contain conventional additives,which can be introduced into the composition in the thermoplastic resin,the rubber, or in the blend before, during or after curing. Examples ofsuch additives are antioxidants, processing aids, reinforcing andnon-reinforcing fillers, pigments, waxes, rubber processing oil,extender oils, antiblocking agents, antistatic agents, ultravioletstabilizers, plasticizers (including esters), foaming agents, flameretardants and other processing aids known to the rubber compoundingart. Such additives may comprise from about 1 to about 300 percent byweight based on the weight of the total polyolefins and rubber in thefinal thermoplastic elastomer product. Fillers and extenders, which canbe utilized, include conventional inorganics such as calcium carbonate,clays, silica, talc, titanium dioxide, carbon black and the like. Therubber processing oils generally are paraffinic, naphthenic or aromaticoils derived from petroleum fractions. The type will be that ordinarilyused in conjunction with the specific rubber or rubbers present in thecomposition, and the quantity of processing oil based on the totalrubber content of the thermoplastic elastomer may range from zero or 50to several hundred parts by weight per hundred parts by weight ofrubber. Important to the efficiency of the catalyst is that the oils andother additives contain no or very low concentrations of compounds thatinterfere with the activity of the catalyst. These include phosphines,amines, sulfides or other compounds that may be classified as Lewisbases.

[0040] The rubber component of the thermoplastic elastomer is generallypresent as small, i.e. micron-size particles within a continuousthermoplastic resin matrix, although a co-continuous morphology or aphase inversion is also possible depending upon the amount of rubberrelative to plastic and the degree of cure of the rubber. The rubber isdesirably at least partially crosslinked, and preferably is completelyor fully crosslinked. It is preferred that the rubber be crosslinked bythe process of dynamic vulcanization. As used in the specification andclaims, the term “dynamic vulcanization” means a vulcanization or curingprocess for a rubber blended with a thermoplastic resin, wherein therubber is vulcanized under conditions of shear at a temperature at whichthe mixture will flow. The rubber is thus simultaneously crosslinked anddispersed as fine particles within the thermoplastic resin matrix,although as noted above other morphologies may exist. Dynamicvulcanization is effected by mixing the thermoplastic elastomercomponents at elevated temperatures in conventional mixing equipmentsuch as multiple-roll roll mills, Banbury mixers, Brabender mixers,continuous mixers, mixing extruders and the like. Generally after areasonably homogenous mixture of the two phases is established, thecuratives are added. Mixing is continued until maximum mixing torque isreached. Thereafter mixing is continued one or two minutes. The uniquecharacteristics of dynamically cured compositions is that,notwithstanding the fact that the rubber component is partially or fullycured, the compositions can be processed and reprocessed by conventionalplastic processing techniques such as extrusion, injection molding andcompression molding. Scrap or flashing can be salvaged and reprocessed.

[0041] It is preferred to prepare a dynamic vulcanizate as describedabove when using peroxide, sulfur, and the phenolic curatives. Peroxidecuratives may cause some chain scission of polyolefins. Thefunctionalized polyolefin is generally, but not necessarily, added aftercuring the rubber phase, to avoid any chemical interaction between thecurative and the functional groups of the functionalized polyolefin. Theaddition of the functionalized polyolefin can occur in the sameequipment or separate equipment from the preparation of thethermoplastic vulcanizate. The polyolefin with the low crystallinity andlow flexural modulus can be added in any stage of the processing, e.g.before or after curing the rubber phase. Commercial thermoplasticvulcanizates can be converted to thermoplastic vulcanizates withexcellent adhesion to textile fibers, by adding during melt blendingappropriate amounts of functionalized polyolefin and polyolefin with lowcrystallinity and low flexural modulus.

[0042] As the hydrosilylation crosslinking system does not appreciablyreact with maleic anhydride functionalized polyolefin, thefunctionalized polyolefin can be added before the crosslinking (curing)step eliminating the extra addition step after crosslinking.

[0043] The polar polymer can be any polymer more polar than polyolefins.The polar polymer can be a molded or shaped article onto which athermoplastic coating is applied or it may be in the form of sheets orfibers. Desirably the polar polymer and the fiber or sheet reinforcementmay be any high tensile modulus material (e.g. above 130,000 psi, moredesirably above 180,000 psi) that can desirably be formed into fibers orsheets. Examples include polyesters, polyamides, glass fibers, naturalfibers such as cellulosic, etc. The fibers can be woven, bundled, yarns,non-woven, etc. In addition polyolefin polymers may be used to make thefibers or blends of polyolefins and the polar polymers may form thefibers, or blends of polyolefin fibers and polar polymer fibers may beused.

[0044] The hot melt adhesive or the thermoplastic vulcanizate of thisdisclosure also adheres well to metallic substrates. Thus they may beused as a coating on metallic parts, sheets, or fibers (wires) or usedto form molded or shaped parts that include metal such as sheets orwires as part of or adhered to a molded or shaped article. Examples ofproducts formed with these thermoplastic vulcanizates include covers forhydraulic hoses, tube and cover for fire fighting hoses, belting,roofing, etc.

EXAMPLES

[0045] The results reported in Tables II-VI were prepared by meltblending the added components to a preformed thermoplastic vulcanizatedescribed in Table I. The results in Table VII was a simple hot meltadhesive formed by melting a polyolefin and a functionalized polyolefin.The compositions in Tables VIII and IX were prepared by adding thefunctionalized polyolefin before crosslinking with a catalyzedhydrosilylation crosslinking agent.

[0046] Table I is a formulation for a generic thermoplastic vulcanizate.The thermoplastic vulcanizate is conventionally prepared as described inU.S. Pat. No. 4,130,535. TABLE I Thermoplastic Vulcanizate Parts by wt.wt. % EPDM rubber 100 30.7 Polypropylene 41 12.6 Stannous Chloride 1.30.4 Extender Oil 130 39.9 Clay 42 12.9 Zinc Oxide 2.0 0.6 Phenolic Resin4.5 1.4 Wax 5.0 1.5 Total 325.8 100

[0047] Various commercially available functionalized polyolefins wereadded in various amounts to thermoplastic vulcanizate prepared accordingto the recipe of Table I. The examples were prepared by compressionmolding the blend of the functionalized polyolefin and the thermoplasticvulcanizate to a nylon 6,6 and polyester fiber blend substrate at 425°F. for 5 minutes of a 15 minute cycle time. TABLE II 180° Peel StrengthVersus Level of Three Different Functionalized Olefins PartsFunctionalized Fusabond ™ Polyolefin* PMD-353D Polybond 300 Bynel ™41E558 32.6  8 pli — — 48.9 13  9 pli — 61.4 12  8  6 pli 81.5 17 — —97.7 15 14  9 130.3  — — 13

[0048] TABLE III 90° Peel Strength Versus Level of Three DifferentFunctionalized Olefins Parts Fusabond ® Functionalized PMD- Polybond ™Bynel ™ Exxelor ™ Polyolefin* 353D 3000 41E558 NDEX 94-6 32.6  6.5 pil 9 pli — — 48.9 11  8 —  6 pli 65.2 11  9  7 pli 12 81.5 26 11 — 11 97.736 11  9 — 130.3  — — 18 —

[0049] As can be seen from Tables II and III Fusabond® PMD-353D givesgreater increases in adhesion than the other three functionalizedpolyolefins, especially when the object is to achieve adhesion above 10or 12 pli (pounds per linear inch). Fusabond® PMD-353D is a maleicanhydride functionalized polypropylene random copolymer which isadvertised as being 1.5% by weight grafted maleic anhydride by itsmanufacturer Dupont Canada, Inc.

[0050] Tables IV and V were prepared to determine the effect of thevarious functionalized polyolefins on critical properties such as ShoreA hardness elongation at break by ASTM D2240, and 100% modulus. TABLE IVShore A Hardness Versus Level of Four Functionalized Polyolefins PartsFunctionalized Fusabond ® Polybond ™ Bynel ™ Exxelor ™ Polyolefin*PMD-353D 3000 41E558 NDEX 94-6 32.6 71 78 — — 48.9 73 83 — 82 65.2 81 8672 86 81.5 87 90 — 89 97.7 88 93 76 — 130.3  — — 80 —

[0051] TABLE V Elongation at Break (%) Versus Level of FourFunctionalized Polyolefins Parts Functionalized Fusabond ® Polybond ™Bynel ™ Exxelor ™ Polyolefin* PMD-353D 3000 41E558 NDEX 94-6 32.6 320325 — — 48.9 315 380 — 375 65.2 380 400 460 380 81.5 355 250 — 300 97.7430 120 480 — 130.3  — — 580 —

[0052] TABLE VI 100% Modulus Versus Level of Four FunctionalizedPolyolefins Parts Functionalized Fusabond ® Polybond ™ Bynel ™ Exxelor ™Polyolefin* PMD-353D 3000 41E558 NDEX 94-6 32.6  620 psi  650 psi — —48.9  700  800 — 750 psi 65.2  790  960 500 psi 880 81.5  910 1100 — 94097.7 1010 1240 550 — 130.3  — — 600 —

[0053] An adhesion value of at least 12 pli was desired with minimalchanges on Shore A hardness, tensile strength and 100% modulus. Thepreferred functionalized polyolefin was Fusabond® PMD353D, which allowedcompositions to meet the 12 pli value with as little as 48.9 or 65.2parts by weight of Fusabond® based upon 100 parts by weight of therubber as shown in Tables II and Ill. The next best functionalizedpolyolefin was Polybond® 3000, a 1.0 to 1.5% maleic anhydride modifiedisotactic polypropylene which was used at the 65.2 or 81.5 parts byweight level to achieve 12 pli adhesion. The other functionalizedpolyolefins were less effective.

[0054] Generally, as seen in Tables IV and VI, all the functionalizedpolyolefins increased the Shore A hardness and 100% modulus of theexamples, Exxelor™ NDEX 94-6 had less effect on these tests than theother materials. The elongation at break (Table V) varied with theamount of functionalized polyolefin.

[0055] The fact that less Fusabond® PMD353D can be used and still meetthe 12 pli adhesion value means it is a preferred functionalizedpolyolefin. Bynels® contribution to hardness was less due to itspolyethylene backbone. The Exxelor™ and Polybond® systems became brittleat higher loadings as seen by their lower elongation at break values athigher loadings.

[0056] While the compression molded samples could meet the 12 pliadhesion requirement, compression molding does not emulate extrusion(sheet or cross-head) sufficiently well to duplicate adhesion values incommercial fiber reinforced hose production. Extrusion is typically usedin the hose industry. When the samples with 48.9 parts by weight ofFusabond® in the previous tables were fabricated into parts byextrusion, the adhesion values fell to values from 10 or 13 pli (TablesII and III) to 6 pli.

[0057] A series of polypropylenes were formulated as hot-melt adhesiveswith Fusabond® P-353MD to determine if adhesion could be furtherincreased by modifying the polypropylene. The melt flow (measured ing/10 min) and the Peel Strength of the various polypropylenes blends areincluded in Table VII below as it was initially postulated that highermelt flow polyethylenes would better adhere to textile fibers due toincreased flow and better wetting. TABLE VII Melt Flow of VariousPolypropylenes and Peel Strength of Their 85:15 Blends with Fusabond ®Melt Flow Peel Strength of Blend Equistar 51S07A 1 12 Rexflex W105 2 18PD9272 3 18 Esc 7032 (Impact PP) 4.5 12 Fina 94-21 (Random PP) 5 23Rexflex W107 10 17 Rexflex W101 14 50 FP200 20 20 Adflex KS357P 25 48FP300 30 24

[0058] The polymer blends from Rexflex® W101 from Huntsman and Adflex®KS357P from Montell gave dramatically superior adhesion to Nylon 6/6woven fabric than the other polypropylene blends. The samples wereprepared by compression molding at 425° F. for 5 min. as part of a 15min cycle. Surprisingly, there was no correlation between melt flow andadhesion. The two superior polypropylenes were differentiated from theothers based upon low crystallinity and lower flexural modulus. Thecrystallinity of Rexflex® W10 1 was 12-18 and the crystallinity ofAdflex® KS357P was 15-20 wt. %. The flexural modulus (tangent) ofRexflex® W101 was 8,000-15000 psi and the flexural modulus (tangent) ofAdflex® KS357P was 10,000-17,000 psi.

[0059] The following Table VIII illustrates two thermoplasticvulcanizates (one with a Shore A hardness of 65 and another with 85)with excellent adhesion to textile fibers. The EPDM rubber is Exxon VX1696 having about 0.7 wt. % of 5-vinyl-2-norborne as the dienecomponent. The first PP (polypropylene) is Rexflex® W101 available fromHuntsman. It is a low crystallinity and low flexural modulus polyolefin.The second PP is a conventional polypropylene with a melt flow of 5.0.Fusabond® is the functionalized polyolefin as previously described. Thesilicon hydride 2-2822 is a hydrosilylation crosslinker available fromDow Corning. The Pt catalyst is PC 085 available from United ChemicalsTechnology. The platinum catalyst solution is only 1.1 wt. % active inoil and only 2 wt. % of the catalyst is Pt. Therefore, the amount ofcatalyst in the recipe is specified by 11 ppm of Pt metal. TABLE VIIITPV CC8E3068 and CC8E3085 65 Shore A 85 Shore A CC8E3068 CC8E3085Textile bondable W8F800-01 W8F801-01 TPVs ingredients Parts Wt. % partsWt. % EPDM rubber* 200 49.0% 200 41.4% First PP Rexflex ® 60.1 14.7%73.7 15.3% Second PP 32.0 7.9% 98.1 20.3% Fusabond ® PMD 353-D 61.115.0% 73.7 15.3% Clay 6 1.5% 30.5 6.3% Oil, Sunpar LW150M 41.1 10.2% 00.0% Silicon Hydride 2-2822 2 0.5% 20.4% Pt Catalyst Solution 5 1.2% 51.0% TOTAL 407.7 100.0% 482.9 100.0%

[0060] These two materials were compounded using a one-step process on a53 mm twin screw extruder. The one step process means the functionalizedpolyolefin was added and blended with the other component beforecrosslinking occurred. These two materials have demonstrated excellentadhesion to both untreated nylon 6/6 and polyester woven fibers. The3068 formulation demonstrated 27 pli peel strength to polyester fibersand 28 pli peel strength to the nylon 6/6 fibers. The 3085 formulationdemonstrated 35 pli peel strength to the polyester fibers and 24 plipeel strength to the nylon 6/6 fibers.

[0061] Another formulation TPV 13067-10 in Table IX below having a 65Shore A hardness was prepared using a twin screw extruder and adding thefunctional polyolefin in a second pass after curing the rubber. The lowcrystallinity and low flexural modulus polyolefin was already present inthe TPV. Compression molded samples of this material had adhesion of 18pli to polyester fiber and 22 pli to nylon 6/6 fiber. Then the materialwas extruded with nylon 6/6 using cross-head extruder. The extrudedsample had an adhesion value of 25 pli to the nylon 6/6 fibers, wellexceeding the hose industries' 12 pli minimum adhesion, and thisconfirmed the positive laboratory results of 22 pli adhesion to nylon6/6 using compression molding. TABLE IX TPV 13067-10 FormulationIngredient Chemical WT. % Exxon VX 1696 EPDM Rubber (VNB) 48.7 RexeneW-101 Low viscosity-Low Modulus 14.6 Polyolefin Fina EOD 94-21 RandomCopolymer (high ethylene 7.8 content) Fusabond PMD 353D Maleic anhydridemod. atactic PP 15 Fluid 2-2822 SiH curative 0.5 Sunpar LW150M Oil 1.2PC 085 Catalyst 0.0012 Irganox B215 AO stabilizer 0.17 KemamideProcessing Aid 0.44 Sunpar LW150M Oil 7.3 Magnesium CarbonatePartitioning Agent 1.4

[0062] Table X illustrates two butyl rubber based thermoplasticelastomers wherein the butyl rubber was cured by hydrosilylationcrosslinking. Bayer XL 1000 is believed to be a terpolymer ofisobutylene, isoprene, and divinylbenzene with the isobutylene beingabout 95 wt. % or more and the other two monomers only providingcrosslinking sites. The Rexene W101 and Fusabond PMD 353D can be addedprior to crosslinking the butyl rubber as there is little interactionbetween the hydrosilylation crosslinking agent and the functionatizedpolyolefin (Fusabond PMD 353D) TABLE X Butyl Rubber based TextileBondable Formulations 13080-05 13080-06 Level (phr) Level (phr) RawMaterial Bayer XL 10000 (butyl 100. 100 rubber) Clay 5.98 6.04 Fina94-21 (PP) 31.96 85.20 Rexene W101 66.18 63.90 Fusabond PMD353D 54.9063.90 SiH 2.01 1.99 Pt Catalyst 5.00 5.00 Sunpar 150 oil #1 63.38 64.47Sunpar 150 oil #2 36/60 35.50 Total 366.01 426 Properties UTS (psi) 7641016 Elongation (%) 402 445 100% Modulus 462 633 Hardness (Shore A) 6980 Tension Set 23 30 Adhesion (180) (pli) Nylon 6,6 fiber 28 39Polyester fiber 31 34

[0063] Table XI below shows a thermoplastic vulcanizate according tothis disclosure that was cured with peroxide (VulKup 40%) and thenblended with Rexflex W101 (a low flexural modulus polyolefin) andFusabond PMD 353D (a maleic anhydride functionalized polyolefin). Theresulting product had excellent adhesion to nylon 6,6 and polyesterfiber. TABLE XI Peroxide Cured Textile Bondable Formulations 13082-10Raw Material Level (phr) MDV95-1-2 140 Equistar 51S07A (PP isotactic) 42White Oil 35 Stanwhite 500 (CaCO₃) 42 TAC (50%) tri-allyl cyanuarate 3.3Vulkup 40 KE (40% active) bis- 1.6 (tertiary butyl)diisopropylbenzeneRexflex W101 56.55 Fusabond PMD353D 56.55 Total 377 Adhesion (180) (pli)Nylon 6,6 fiber 23 Polyester fiber 22

[0064] The thermoplastic vulcanizate compositions of this disclosure areuseful as matrix materials for a variety of fiber and/or metalreinforced materials such as hoses, tubing, fiber reinforced sheeting ormembranes, belting, wire reinforced articles, metal rubber composites,etc. The blends of low flexural modulus polyolefin and functionalizedpolyolefin are useful as thermoplastics with excellent adhesion tomolded articles, textile fibers, and/or metal or as adhesives, eitheralone or used to bond a thermoplastic vulcanizate to a high modulusfiber or sheet.

[0065] While in accordance with the Patent Statutes, the best mode andpreferred embodiment have been set forth, the scope of the invention isnot limited thereto, but rather by the scope of the attached claims.

What is claimed:
 1. A thermoplastic elastomer having adhesion to metal,molded polar polymers and textile fibers, said thermoplastic elastomercomprising; a) a dynamically crosslinked rubber, b) from about 20 toabout 400 parts of a first polyolefin having from about 10 to about 26.5weight percent crystallinity and a flexural modulus (tangent) from about5,000 psi (34.5 MPa) to about 20,000 psi (1 38 MPa), and c) from about10 to about 200 parts by weight a functionalized polyolefin havingpendant polar functional groups, wherein said polar functional groupsare present on from about 0.5 to about 3.5 mole percent of the totalrepeating units of said functionalized polyolefin and saidfunctionalized polyolefin is derived from polymerizing at least onemonoolefin into a semicrystalline polymer or is derived fromhydrogenating the polydiene blocks of a block copolymer, and whereinsaid parts by weight are based upon 100 parts by weight of crosslinkedrubber.
 2. A thermoplastic elastomer according to claim 1 furtherincluding a semicrystalline polyolefin having a flexural modulus(tangent) of at least 45,000 psi (310 MPa).
 3. A thermoplastic elastomeraccording to claim 2, wherein said polyolefin with low crystallinity andlow flexural modulus is from about 15 to about 85 parts by weight per100 parts by weight of the total semicrystalline polyolefins and whereinsaid functionalized polyolefin is from about 10 to about 60 parts byweight per 100 parts of polyolefins.
 4. A thermoplastic elastomeraccording to claim 3, wherein said polar functional groups are presentin an amount from about 1 to about 2.5 mole percent of the total repeatunits of said functionalized polyolefin.
 5. A thermoplastic elastomeraccording to claim 3, wherein said pendant polar functional groups arederived from grafting maleic anhydride to a polyolefin backbone or to ahydrogenated polydiene block.
 6. A thermoplastic elastomer according toclaim 1, wherein said crosslinked rubber comprises an EPDM rubber or apolymer derived from polymerizing isobutylene and at least one othermonomer or combinations thereof.
 7. A thermoplastic elastomer accordingto claim 1, wherein said crosslinked rubber comprises natural rubber, ahomopolymer of a conjugated diene, or a copolymer having at least 50weight percent repeat units from a conjugated diene, or combinationsthereof.
 8. A thermoplastic elastomer having adhesion to metal, moldedpolar polymers and textile fibers, said thermoplastic elastomercomprising; a) a dynamically crosslinked rubber, b) from about 5 toabout 200 parts of a first polyolefin having at least 80 mole percentrepeating units from a single monoolefin monomer and less than 10 weightpercent crystallinity, and c) from about 10 to about 200 parts by weighta functionalized polyolefin having pendant polar functional groups,wherein said polar functional groups are present on from about 0.5 toabout 3.5 mole percent of the total repeating units of saidfunctionalized polyolefin and said functionalized polyolefin is derivedfrom polymerizing at least one monoolefin into a semicrystalline polymeror is derived from hydrogenating the polydiene blocks of a blockcopolymer, and wherein said parts by weight are based upon 100 parts byweight of crosslinked rubber.
 9. A thermoplastic elastomer according toclaim 8 further including a semicrystalline polyolefin having a flexuralmodulus (tangent) of at least 45,000 psi (310 MPa).
 10. A compositearticle from a thermoplastic vulcanizate and a polar polymer, saidarticle comprising; a) a polar polymer or a metal having a tensilemodulus of at least 130,000 psi and being in the form of a moldedarticle, sheet, or fibers; and b) a thermoplastic vulcanizate including,(1) a crosslinked rubber (2) from about 10 to about 400 parts by weightof a first polyolefin having a flexural modulus from about 5,000 psi toabout 20,000 psi and a crystallinity of from about 10 to about 26.5weight percent, and (3) from about 10 to about 200 parts by weight of afunctionalized polyolefin having pendent polar functional groups,wherein said functional groups are present from about 0.5 to about 3.5mole percent of the total repeating units of said functionalizedpolyolefin and said functionalized polyolefin is derived frompolymerizing at least one monoolefin into a semicrystalline polymer oris derived from hydrogenating the polydiene blocks of a block copolymer,wherein said crosslinked rubber, said functionalized polyolefin, andsaid first polyolefin are interdispersed such that the thermoplasticvulcanizate is melt processable in conventional thermoplastic processingequipment, and wherein said parts by weight are based upon 100 parts byweight of total rubber.
 11. A composite article according to claim 10,wherein said fibers are present in the form of woven or non-wovenfabric.
 12. A composite article according to claim 11, wherein saidfibers comprise a polyester, a polyamide, or polypropylene, or blendsthereof.
 13. A composite article according to claim 10, in the form of amembrane, tube, belting or hose.
 14. A composite article according toclaim 12, in the form of a membrane, tube, belting or hose.
 15. Acomposite article according to claim 10, wherein said fiber and/or sheetof polar polymer id substantially encased in said thermoplasticvulcanizate.
 16. A composite article according to claim 10, wherein saidthermoplastic vulcanizate has adhesion to said polar polymer of at least12 pli by ASTM D 1876-72.
 17. A composite article according to claim 10,wherein said polar polymer is present as fibers of polyester, polyamide,or polypropylene, or blends thereof.
 18. A composite article accordingto claim 10, wherein said functionalized polyolefin comprises maleicanhydride molecules grafted to a polyolefin backbone or to ahydrogenated polydiene block.
 19. A composite article according to claim10, wherein said polar polymer is a polyester, polyamide, orpolyurethane or blend thereof.
 20. A composite article from athermoplastic vulcanizate, said article comprising; a) a polar polymeror a metal having a tensile modulus of at least 130,000 psi and being inthe form of a molded article, sheet, or fibers; and b) a thermoplasticvulcanizate including, (1) a crosslinked rubber (2) from about 5 toabout 200 parts by weight of a first polyolefin having at least 80 molepercent of repeating units from a single monoolefin monomer andcrystallinity of less than 10, and (3) from about 10 to about 200 partsby weight of a functionalized polyolefin having pendent polar functionalgroups, wherein said functional groups are present from about 0.5 toabout 3.5 mole percent of the total repeating units of saidfunctionalized polyolefin and said functionalized polyolefin is derivedfrom polymerizing at least one monoolefin into a semicrystalline polymeror is derived from hydrogenating the polydiene blocks of a blockcopolymer, wherein said crosslinked rubber, said functionalizedpolyolefin, and said first polyolefin are interdispersed such that thethermoplastic vulcanizate is melt processable in conventionalthermoplastic processing equipment and wherein said parts by weight arebased upon 100 parts by weight of rubber.
 21. In process for forming afiber and/or sheet reinforced thermoplastic vulcanizate including; a)contacting a fiber and/or sheet with a thermoplastic vulcanizate inmolten form, b) forming said thermoplastic vulcanizate into a desiredshape and, c) subsequently cooling said thermoplastic vulcanizate; theimprovement wherein said thermoplastic vulcanizate comprises; d) acrosslinked rubber, e) from about 10 to about 400 parts by weight of afirst polyolefin having low crystallinity from about 10 to about 26.5weight percent and low flexural modulus from about 5,000 psi to about20,000 psi, and f) from about 10 to about 200 parts by weight afunctionalized polyolefin having pendant polar functional groups,wherein said polar functional groups are present on from about 0.5 toabout 3.5 mole percent of the total repeating units of saidfunctionalized polyolefin and said functionalized polyolefin is derivedfrom polymerizing at least one monoolefin into a semicrystalline polymeror is derived from hydrogenating the polydiene blocks of a blockcopolymer, wherein said parts by weight are based upon 100 parts byweight of crosslinked rubber, wherein said polyolefin having a lowcrystallinity and low flexural modulus is present from about 10 to about350 parts by weight per 100 parts by weight of total semicrystallinepolyolefins and said functionalized polyolefin is present from about 5to about 75 parts by weight per 100 parts by weight of totalsemicrystalline polyolefins.
 22. A hot-melt composition with adhesion topolar polymer, said composition comprising: a) from about 20 to about 90parts by weight of a first polyolefin with crystallinity from about 10to about 26.5 weight percent and a flexural modulus from about 5000 toabout 20000 psi and, b) from about 10 to about 60 parts by weight of afunctionalized polyolefin having from about 0.5 to about 3.5 molepercent of functional groups based upon total repeating units in saidfunctionalized polyolefin and said functionalized polyolefin is derivedfrom polymerizing at least one monoolefin into a semicrystalline polymeror is derived from hydrogenating the-polydiene blocks of a blockcopolymer.
 23. A process for preparing a thermoplastic vulcanizatehaving adhesion to metal and polar polymers, said process comprising a)blending a functionalized polyolefin having from about 0.5 to about 3.5mole percent of polar functional groups with a thermoplasticvulcanizate, wherein, if said thermoplastic vulcanizate does not includeat least 10 parts by weight of a first polyolefin having from about 10to about 26.5 weight percent crystallinity and a modulus from about5,000 psi to about 20,000 psi, further including blending in from about10 to about 400 parts of said first polyolefin.